Process for the production of polymer microparticles

ABSTRACT

The object of the present invention is to provide a process for producing high-quality polymer microparticles having uniform particle size of the order of several micrometers to tens of micrometers by inverse suspension polymerization at high productivity while keeping excellent dispersion stability without causing aggregation among particles. The process is one for the production of polymer microparticles by inverse suspension polymerization of a vinyl monomer and includes steps of preparing in a dispersing tank a water-in-oil (W/O) type emulsion in which an organic solvent is a continuous phase and an aqueous solution of a vinyl-based monomer is a dispersing phase, and conducting the inverse suspension polymerization while feeding the water-in-oil (W/O) type emulsion to a continuous stirred tank reactor.

FIELD OF THE INVENTION

The present invention relates to a method for producing polymermicroparticles. More specifically, the present invention relates to amethod for producing high-quality polymer microparticles uniform inparticle size having a specific range of particle size by inversesuspension polymerization using a continuous stirred tank reactor of anemulsionized vinyl-based monomer in a dispersing tank, at highproductivity, without causing aggregation of particles and in a stableeven if the scale is increased.

BACKGROUND ART

Micron-sized spherical polymer microparticles are utilized for cosmeticadditives, supports for various chemical materials, spacers, columnpackings for chromatography, light diffusion agents, porosificationagents, weight-lightening agents, antiblocking agents, surfacemodification agents for recording paper, and the like.

Among these, hydrophilic crosslinked polymer microparticles can be usedas a hydrous gel microparticle, and is useful as cosmetics additives,supports, porosification agents, weight-lightening agents, and surfacemodification agents for recording paper.

Production of polymer particles by inverse suspension polymerization ofa vinyl-based monomer has conventionally been carried out. Astechnologies of producing hydrophilic crosslinked polymer particles byinverse suspension polymerization, there have been known a method inwhich a water-in-oil microdispersed droplet of a monomer is formed usinga compound having a specific HLB as a dispersing agent beforepolymerization and then the monomer is polymerized while dropping it(see Patent Document 1), a method in which inverse suspensionpolymerization is carried out in the presence of a water-absorptivepolymer particle, an oil-soluble polymerization initiator and adispersing agent, and during or after the polymerization a hydrophobicvinyl-based monomer and an oil-soluble polymerization initiator areadded to perform polymerization (see Patent Document 2), a method inwhich a hydrophilic vinyl-based monomer is inverse suspensionpolymerized in the presence of a silicone compound having at least onefunctional group in the reaction system (see Patent Document 3), and thelike.

However, these conventional techniques include a semi-batchwiseoperation, which has an intermediate character between batchwise (batch)operation and continuous operation. Therefore, there are problems thatthe dispersion stability of polymer particles during or afterpolymerization is not sufficient, the particle size of polymer particlesobtained is nonuniform, and the hydrophilicity of polymer particlesobtained is degraded. In particular, when hydrophilic particles with ahigh degree of crosslinking are produced while increasing the proportionof a multifunctional vinyl-based monomer used, polymerization stabilityis significantly degraded, and problems such as aggregation ofparticles, degradation in the quality of polymer particles obtained, anda reduction in productivity easily occur.

Since all the above-mentioned production methods are ones in whichpolymerization is performed by feeding a monomer emulsion continuouslyover one hour or more to a reactor heated to a high temperature of 70°C. or higher without discharging polymer microparticles, and agingnaturally in the tank, aggregation of particles or the like easilyoccurs and the particle size of the resulting polymer particles becomesirregular. In addition, when a large amount of a crosslinking agent suchas a multifunctional vinyl-based monomer, is used, most part ofunreacted crosslinking agent becomes easy to flow out into a continuousphase side, and when polymerization is continued in this state,particles aggregate more and this is expected to lead to theaforementioned deterioration in quality of polymer particles.

Furthermore, Patent Document 4 discloses an absorptive polymer particlewhich is produced by inverse suspension polymerization using a redoxpolymerization initiator for the production of a water absorptivepolymer having a specific water absorptivity, and a polymer particle isproduced by feeding tert-butyl hydroxyperoxide which is an oil-solubleoxidizing agent, and then feeding sodium bisulfite which is awater-soluble reducing agent.

According to this production method, particle size control ofmicroparticles can be performed more precisely in comparison toaforementioned conventional technologies. Since a polymerizationreaction occurs before the water-soluble reducing agent is diffusedsufficiently, this is not satisfactory as a method for producing ahigh-quality particle that is uniform in particle size and has aparticle size falling within a specified range, in a stable statewithout causing, for example, aggregation of particles.

The above-mentioned conventional method is a batch production system.Therefore, when larger amount of a monomer is charged for one timereaction, its reaction liquid is brought to a boil by polymerizationheat, and then, inside of the reactor is pressurized, being dangerous.Accordingly, it is required to produce it within safe limits whilecontrolling a balance between polymerization heat and heat capacity of araw material including a solvent, water, and the monomer, and there hasbeen a problem that the method has low productivity because the amountof obtained product one time reaction is restricted to low.

Meanwhile, a continuous polymerization apparatus with a reactorcontaining a dispersion medium therein as well as a monomer feed portlocated at the top of the reactor and a polymer discharge port at thebottom of the reactor are provided is known in Patent Document 6,related to continuation of suspension polymerization to increaseproductivity.

However, the above-mentioned reactor is a tubular reactor and has astructure that does not stir its content during polymerization, which isunsuitable for the continuous inverse suspension polymerization.Therefore, the reactor is not an apparatus capable of producinghigh-quality polymer microparticles having uniform particle size in aparticular diameter range.

With regard to the definition of a reaction apparatus, the continuousoperation is an operating method in which a raw material for thereaction is continuously supplied from an inlet port of the reactor andthe product is continuously drawn from an outlet port of the reactor,and the both tank and tubular reactors can be operated continuously, asdescribed in “Han-no Kogaku” (Baifukan Co., Ltd). Meanwhile, thesemi-batchwise operation has an intermediate character between batchwiseoperation and continuous operation. For example, when one component B ofa raw material is charged into a vessel type reactor in advance, andthen, another raw material component A is continuously or intermittentlyflowed into the reactor to progress the reaction, it is considered thatthe reaction is a batchwise operation for the component B, and thereaction is a continuous operation for the component A. Therefore,techniques in Patent Documents 1 to 3 include a semi-batchwiseoperation.

Patent Document 1: JP-A H05-222107

Patent Document 2: JP-A 2003-301019

Patent Document 3: JP-A 2003-34725

Patent Document 4: JP-A 2004-262747

Patent Document 5: JP-A H09-43898

DISCLOSURE OF THE INVENTION Problems That the Invention is To Solve

The object of the present invention is to provide a method for theproduction of high-quality polymer microparticles uniform in particlesize having a particle size of the order of several micrometers to tensof micrometers at high productivity while keeping excellent dispersionstability without causing aggregation of particles by continuous inversesuspension polymerization using a continuous stirred tank reactor.

In particular, the present invention is one to provide a method in whichhigh-quality polymer microparticles uniform in particle size can besmoothly produced at high productivity while keeping high polymerizationstability and suspension stability even if hydrophilic particles havinga high degree of crosslinking are produced.

Means For Solving the Problems

The present inventors have engaged in an intensive investigation inorder to attain the above objects. The inventors have studied conditionsin particular for the continuous inverse suspension polymerization whichis more excellent in productivity than conventional batch productionsystem when the vinyl-based monomer is subjected to inverse suspensionpolymerization for the production of polymer microparticles. As aresult, when a vinyl-based monomer and the like are emulsified intowater-in-oil (W/O) state in a dispersing tank, in advance, and then, theemulsion is subjected to continuously polymerization in a continuousstirred tank reactor, it is found that high-quality spherical particleshaving a particle size of the order of several micrometers to tens ofmicrometers and being uniform in particle size can be produced at higherproductivity while keeping excellent dispersion stability andpolymerization stability without causing aggregation, clumping, andadhesion to a polymerization apparatus of polymer particles during orafter polymerization.

The present invention for solving the above-mentioned problems is asfollows.

The first invention is a method for the production of polymermicroparticles by inverse suspension polymerization of a vinyl-basedmonomer, characterized by preparing in a dispersing tank a water-in-oil(W/O) type emulsion in which an organic solvent is a continuous phaseand an aqueous solution of a vinyl-based monomer is a dispersing phase,and conducting the inverse suspension polymerization while feeding thewater-in-oil (W/O) type emulsion to a continuous stirred tank reactor.

The second invention is a method for the production of polymermicroparticles according to the first invention, wherein a redoxpolymerization catalyst is used as a polymerization initiator.

The third invention is a method for the production of polymermicroparticles according to the second invention, wherein an oxidizingagent in the redox polymerization catalyst is an oil-soluble oxidizingagent.

The fourth invention is a method for the production of polymermicroparticles according to any one of the first to third inventions,wherein a reaction tank having at least two continuous stirred tankreactors serially-connected is used.

The fifth invention is a method for the production of polymermicroparticles according to any one of the first to fourth inventions,wherein a residence time of a reaction liquid in at least first reactiontank is ten minutes or shorter.

The sixth invention is a method for the production of polymermicroparticles according to any one of the first to fifth inventions,wherein a ratio of the dispersing phase in each reaction liquid in therespective reaction tank is 30% or less by volume.

The seventh invention is a method producing polymer microparticlesaccording to any one of the first to sixth inventions, wherein thewater-in-oil (W/O) type emulsion is prepared using a dispersing tankwhich has at least one stirring apparatus and at least one membraneemulsification apparatus.

The eighth invention is a method producing polymer microparticlesaccording to any one of the first to seventh inventions, wherein thewater-in-oil (W/O) emulsion is deaerated in any step after passing themembrane emulsification apparatus.

The ninth invention is a method for the production of polymermicroparticles according to any one of the first to eighth inventions,wherein a continuous phase component is continuously fed to a wall of agas phase of the continuous stirred tank reactor.

The tenth invention is a method for the production of polymermicroparticles according to any one of the first to ninth inventions,wherein an oxidizing agent or a reducing agent is mixed with thewater-in-oil (W/O) emulsion in the dispersing tank.

The eleventh invention is a method for the production of polymermicroparticles according to any one of the first to tenth inventions,wherein a water-in-oil (W/O) emulsion is prepared which has an averageparticle size of the dispersing phase of 100 μm or less in thedispersing tank.

The twelfth invention is a method for the production of polymermicroparticles according to any one of the first to eleventh inventions,wherein a macromonomer having a radically polymerizable unsaturatedgroup at an end of a polymer derived from a vinyl-based monomer is usedas a dispersion stabilizer.

The thirteenth invention is a method for the production of polymermicroparticles according to any one of the first to twelfth inventions,wherein at least one part of the vinyl-based monomer has a polar groupselected from the group consisting of a carboxyl group, a sulfone groupand an amide group.

The fourteenth invention is a method for the production of polymermicroparticles according to any one of the first to thirteenthinventions, wherein the vinyl-based monomer contain a multifunctionalvinyl monomer having two or more radical polymerizable unsaturatedgroups.

The fifteenth invention is a method for the production of polymermicroparticles according to the fourteenth invention, wherein a molarratio of a monofunctional vinyl monomer and the multifunctional vinylmonomer is 100:0.1 to 100:10.

The sixteenth invention is a method for the production of polymermicroparticles according to any one of the first to fifteenthinventions, wherein the polymer microparticle produced by inversesuspension polymerization are polymer microparticles having acrosslinking density of 0.5% or more by mol.

The seventeenth invention is a method for the production of polymermicroparticles according to any one of the first to sixteenthinventions, wherein the polymer microparticles produced by inversesuspension polymerization are polymer microparticles which have anaverage particle size in a saturated water-swollen state of 2 to 100 μm,and a content ratio of particles having a particle size of 150 μm orlarger in a saturated water-swollen state of 1.0% or less by weight.

The eighteenth invention is a method for the production of polymermicroparticles according to any one of the first to sixteenthinventions, wherein the polymer microparticles produced by inversesuspension polymerization are polymer microparticles which have a waterabsorption ratio of 5 to 50 times, an average particle size in asaturated water-swollen state of 5 to 70 μm, and a content ratio ofparticles having a particle size of 150 μm or larger in a saturatedwater-swollen state of 0.3% or less by weight.

Effect of the Invention

According to the production method of the present invention,high-quality spherical hydrophilic polymer microparticles remarkablyhigher uniform in particle size than those by conventional technologiescan be produced at high productivity while keeping high dispersionstability and polymerization stability without causing aggregation,clumping and adhesion to a polymerization apparatus of particles duringor after polymerization, in comparison with a batch-wise process.Moreover, according to the production method of the present invention,even if hydrophilic particles having a high degree of crosslinking areproduced using a large amount of a multifunctional vinyl-based monomer,high-quality hydrophilic crosslinked polymer microparticles uniform inparticle size can be produced without causing aggregation, clumping andadhesion to a polymerization apparatus of particles. Furthermore, whenthe production is carried out under conditions of an increased scale forincreasing the productivity, the production method of the presentinvention can lead to high-quality polymer microparticles.

Since the polymerization reaction can be conducted in a reactor having asmaller volume than that of batch production system according to thecontinuous inverse suspension polymerization of the present invention,polymer microparticles having particle size distribution with a sharppeak can be obtained.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a microscope photograph of polymer microparticles RT-1 (afterpolymerization, in-oil dispersion);

FIG. 2 is a microscope photograph of polymer microparticles RT-1 (afterpolymerization, in-water dispersion); and

FIG. 3 is a microscope photograph of polymer microparticles RT-2 (afterpolymerization, in-oil dispersion);

FIG. 4 is a microscope photograph of polymer microparticles RT-2 (afterpolymerization, in-water dispersion);

FIG. 5 is a diagram showing an apparatus for the measurement of thewater absorption ratio of polymer microparticles; and

FIG. 6 is a flow diagram showing serially-connected continuous stirredtank reactors.

BEST MODE FOR CARRYING OUT THE INVENTION

1: burette, 2: pinch cock, 3: silicone tube, 4: polytetrafluoroethylenetube, 5: funnel, 6: sample (polymer microparticles), 7: filter paper forfixing sample (polymer microparticles), 8: supporting cylinder, 9:adhesive tape, 10: filter paper for device, 11: lid, 12: ion exchangewater,

13: first dispersing tank, 14: second dispersing tank, 15: firstreaction tank, 16: second reaction tank, 17: third reaction tank, 18:oil phase supplying pipe, 19: aqueous phase supplying pipe, 20:oxidizing agent supplying pipe, 21: reducing agent supplying pipe, 22:additional catalyst supplying pipe, 23: additional catalyst supplyingpipe, 24: polymer microparticles solution sending pipe, 25: oil phasecomponent supplying pipe for washing.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the embodiments of the present invention are described indetail.

The “inverse suspension polymerization of a vinyl-based monomer”according to the present invention means a polymerization using an oilphase as a dispersion medium and an aqueous phase as a dispersoid. Ingeneral, in the case where polymerization is performed using ahydrophilic vinyl-based monomer, particles are produced by water-in-oil(W/O) type inverse suspension polymerization in which an aqueous phase(an aqueous solution of the hydrophilic vinyl-based monomer) issuspended in the form of droplets in an oil phase (a dispersion mediumcomposed of a hydrophobic organic solvent).

The inverse suspension polymerization of a vinyl-based monomer in thepresent invention is one in which the vinyl-based monomer is subjectedto inverse suspension polymerization while continuously supplying aprepared water-in-oil type emulsion in advance to the continuous stirredtank reactor and discharging continuously.

In the preferable production method of the present invention, acontinuous reaction apparatus is used shown in FIG. 6, a continuousphase (oil phase) obtained by a dispersion stabilizer and an organicsolvent, and an aqueous solution of a vinyl-based monomer (dispersingphase) are used to prepare a water-in-oil type emulsion in a dispersingtank (13: first dispersing tank and 14: second dispersing tank) inadvance, a dispersion liquid (emulsion) containing an oxidizing agent iscontinuously supplied into a continuous stirred tank reactor (15: firstreaction tank), and then, a reducing agent is supplied to the continuousstirred tank reactor to initiate polymerization. Polymerization reactionis performed by continuously transferring the reaction liquid overflowedfrom the first reaction tank to the second reaction tank, and then, thethird reaction tank. An oxidizing agent is added to the second and thirdreaction tanks to increase a polymerization rate as needed.

The dispersion tank is preferably one having a dispersion tank having atleast one stirring apparatus and a dispersion tank having at least onemembrane emulsification apparatus. For the purpose of preparing awater-in-oil (W/O) type emulsion with uniform particle size, and also, amulti-stage dispersion tank is preferably used.

Examples of the stirring apparatus include a stirring machine havingmixing blades, a homogenizer, a stirring machine using sonication, anemulsifier and the like. Among these, a dispersion tank having anemulsifier and a dispersion tank having a membrane emulsificationapparatus is preferably used in multi-stages.

A dispersed droplet having a certain size is formed using an emulsifierand the size of the vinyl-based monomer drop is adjusted using amembrane emulsification apparatus. A membrane emulsification apparatusis one to pass a water-in-oil (W/O) type emulsion through a hydrophobicmicroporous membrane, and then, to obtain a more microparticulatedwater-in-oil (W/O) type emulsion. The size of the drop of thevinyl-based monomer can be adjusted with a combination of a stirringrevolution speed of the emulsifier and a pore size of the microporousmembrane of the membrane emulsification apparatus. And, polymermicroparticles can be obtained initiating the polymerization by thecontinuous stirred tank reactor.

In the present invention, for the purpose of producing high-qualitypolymer microparticles uniform in particle size having a particle sizeof the order of several micrometers to tens of micrometers, awater-in-oil (W/O) type emulsion having the average size of thedispersing phase of 100 μm or smaller is preferably contained in thedispersing tank.

The vinyl-based monomer for the inverse suspension polymerizationaccording to the present invention is not particularly limited so longas it is a radically polymerizable vinyl-based monomer. For example, ahydrophilic monomer having a hydrophilic group such as a carboxyl group,an amino group, a phosphoric acid group, a sulfonic acid group, an amidegroup, a hydroxyl group, a quaternary ammonium group or the like can beused. Among these, when a monomer having a carboxyl group, a sulfonicgroup or an amide group is used, polymer microparticles high inhydrophilicity and excellent in water absorption capacity andwater-retaining property can be obtained, being preferable.

Specific examples of the hydrophilic vinyl-based monomer include avinyl-based monomer having a carboxyl group or its (partially)alkali-neutralized product, such as (meth)acrylic acid, crotonic acid,itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, monobutylmaleate and cyclohexanedicarboxylic acid; a vinyl-based monomer havingan amino group or its (partially) alkali-neutralized product or its(partially) quaternary product, such asN,N-dimethylaminoethyl(meth)acrylate,N,N-diethylaminoethyl(meth)acrylate,N,N-dimethylaminoepropyl(meth)acrylate, andN,N-dimethylaminopropyl(meth)acrylamide; N-vinylpyrrolidone,acryloylmorpholine; a vinyl-based monomer having a phosphoric acidgroup, or its (partially) alkali-neutralized product, such as acidphosphoxyethyl methacrylate, acid phosphoxypropyl methacrylate, and3-chloro-2-acid phosphoxypropyl methacrylate; a vinyl-based monomerhaving a sulfonic acid group or phosphonic acid group, or its(partially) alkali-neutralized product, such as2-(meth)acrylamide-2-methylpropanesulfonic acid,2-sulfoethyl(meth)acrylate, 2-(meth)acryloylethanesulfonic acid,allylsulfonic acid, styrene sulfonic acid, vinylsulfonic acid,allylphosphonic acid, and vinylphosphonic acid; a nonionic hydrophilicmonomer such as (meth)acrylamide, N,N-dimethyl acrylamide, N-isopropylacrylamide, N-methylol(meth)acrylamide, N-alkoxymethyl(meth)acrylamide,(meth)acrylonitrile, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate and the like. These compounds may be usedsingly or in combination of two or more types thereof.

Using a compound selected from (meth)acrylic acid,(meth)acrylamide and2-acrylamide-2-methylpropanesulfonic acid singly or in combination oftwo or more types for the inverse suspension polymerization ispreferable from the viewpoint that polymerizability is excellent andresulting particles are excellent in water absorption property. Theparticularly preferred is (meth)acrylic acid.

In the present invention, a multifunctional vinyl-based monomer havingtwo or more radically polymerizable unsaturated groups may be used as avinyl-based monomer together with at least one of the above-mentionedmonofunctional hydrophilic vinyl-based monomer for the inversesuspension polymerization.

Therefore, the “vinyl-based monomer” according to the present inventionis a general term for the monofunctional vinyl-based monomer and themultifunctional vinyl-based monomer.

The multifunctional vinyl-based monomer is not particularly limited solong as it has two or more groups radically polymerizable with theabove-mentioned hydrophilic vinyl-based monomer, and specific examplethereof includes a di- or tri- (meth)acrylate of a polyol, such aspolyethylene glycol di(meth)acrylate, polypropylene glycoldi(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropanetri(meth)acrylate, and a tri(meth)acrylate of a modifiedtrimethylolpropane ethylene oxide; a bisamide such asmethylenebis(meth)acrylamide; divinyl benzene, allyl(meth)acrylate, andthe like. These compounds may be used singly or in combination of two ormore types thereof.

Among these, polyethylene glycol diacrylate and methylene bisacrylamideare suitably used as the multifunctional vinyl-based monomer because itexcels in solubility in a mixed liquid of water and a base-forminghydrophilic vinyl-based monomer and it is advantageous in being used inan amount increased for obtaining a high degree of crosslinking. Theparticular preferred is polyethylene glycol di(meth)acrylate.

The amount of the multifunctional vinyl-based monomer to be used dependson the type of the vinyl-based monomer to be used and the intendedapplication of resulting particles. When the polymer particles arerequired to have crosslinked characteristics, the amount thereof ispreferably in the range from 0.1 to 10 mol, more preferably from 0.2 to8 mol, and further preferably from 0.5 to 5 mol based on 100 mol of thetotal amount of the monofunctional vinyl-based monomer to be used.

Examples of the hydrophobic organic solvent that forms an oil phase(dispersion medium) in the inverse suspension polymerization accordingto the present invention include an aliphatic hydrocarbon solvent having6 or more carbon atoms; an aromatic hydrocarbon solvent such as benzenetoluene, xylene and ethyl benzene; a silicone-based solvent such asoctamethylcyclotetrasiloxane, and the like. In particular, hexane,cyclohexane, and n-heptane are suitably used because the solubilities ofvinyl-based monomer and water in the solvent are small and they can beremoved easily after polymerization.

In the inverse suspension polymerization according to the presentinvention, a hydrophilic vinyl-based monomer (and a neutralized saltthereof) is preferably dissolved in water to form an aqueous solutionand then is added to the polymerization system. The concentration of thehydrophilic vinyl-based monomer in the aqueous solution in which thehydrophilic vinyl-based monomer is dissolved is preferably in the rangefrom 5% to 80% by weight, and particularly from 20% to 60% by weightfrom the viewpoint that the inverse suspension polymerization proceedssmoothly and the productivity is good.

In the case where the hydrophilic vinyl-based monomer for the inversesuspension polymerization is a vinyl-based monomer having an acidicgroup such as a carboxyl group and a sulfonic acid group, when thehydrophilic vinyl-based monomer is added to water and the acidic groupin the vinyl-based monomer is neutralized with an alkali aqueoussolution such as aqueous ammonia, an aqueous sodium hydroxide solution,and an aqueous potassium hydroxide solution, an aqueous solution can beprepared in which the vinyl-based monomer is dissolved sufficiently.

In the producing method of the present invention, a dispersionstabilizer is an essential component.

Specific examples of the dispersion stabilizer include a macromonomertype dispersion stabilizer, and a nonionic surfactant such as a sorbitanfatty acid ester, a polyglycerol fatty acid ester, a sucrose fatty acidester, sorbitol fatty acid ester and a polyoxyethylene alkyl ether.

Among these, a macromonomer type dispersion stabilizer is preferable.The macromonomer type dispersion stabilizer is a vinyl-basedmonomer-derived polymer having, at an end thereof, a radicallypolymerizable unsaturated group.

Moreover, it is preferable to use a relatively high hydrophobic nonionicsurfactant having an HLB of 3 to 8, such as sorbitan monooleate andsorbitan monopalmitate, together with a macromonomer type dispersionstabilizer. These surfactants may be used singly or in combination oftwo or more types thereof.

The preferable macromonomer as the above-mentioned macromonomer typedispersion stabilizer are a macromonomer having an a-substituted vinylgroup represented by the following formula (1), at an end of a polymerobtained by radical polymerization of a vinyl-based monomer at atemperature range of 150° C. to 350° C., and/or a macromonomer having a(meth)acryloyl group at an end of a polymer derived from a vinyl-basedmonomer.

H₂C═C(X)—  (1)

(In the formula, X is a monovalent polar group.)

These macromonomers are excellent as a dispersion stabilizer andpreferable. The weight average molecular weight of the macromonomer ispreferably in the range from 1,000 to 30,000. The macromonomerpreferably has both structural units derived from a hydrophilicvinyl-based monomer and a hydrophobic vinyl-based monomer. Thestructural unit derived from the hydrophobic vinyl-based monomer ispreferably a structural unit derived from a (meth)acrylic acid alkylester having 8 or more carbon atoms, and the structural unit derivedfrom the hydrophilic vinyl-based monomer is preferably a structural unitderived from a vinyl-based monomers having a carboxyl group.

In particular, when the hydrophilic particles are produced by theinverse suspension polymerization of a vinyl-based monomer using amacromonomer type dispersion stabilizer, it is preferable to use amultifunctional vinyl-based monomer together with a monofunctionalcompound. Thereby hydrophilic particles having improved strength andshape retainability can be obtained.

The dispersion stabilizer is preferably added to a polymerization systemafter being dissolved or uniformly dispersed in a hydrophobic organicsolvent that is a dispersion medium (oil phase).

The amount of the dispersion stabilizer to be used is preferably in therange from 0.1 to 50 parts by weight, more preferably from 0.2 to 20parts by weight, and further preferably from 0.5 to 10 parts by weightbased on 100 parts by weight of the total amount of the vinyl-basedmonomer in order to obtain hydrophilic polymer microparticles uniform inparticle size while maintaining excellent dispersion stability. If theamount of the dispersion stabilizer used is too small, the dispersionstabilities of the vinyl-based monomer and formed polymer microparticlesin the polymerization system becomes poor, and the formed particleseasily aggregate, precipitate, and have variation in particle size. Onthe other hand, if the amount of the dispersion stabilizer used is toolarge, the amount of the microparticles (having size of 1 μm or smaller)by-produced may be increased.

In the inverse suspension polymerization according to the presentinvention, it is preferable to carry out the polymerization so that theweight ratio of an oil phase (dispersion medium) to an aqueous phase(dispersoid) in the polymerization system may become from 99:1 to 20:80,and particularly 95:5 to 30:70, from the viewpoint that productivity,dispersion stability during polymerization, and control of particle sizeof the polymer microparticles can be satisfied at the same time. It isnoted that the aqueous phase (dispersoid) means a sum of the vinyl-basedmonomer and water before polymerization, and produced polymermicroparticles and water.

In the inverse suspension polymerization, it is required that adispersion stabilizer is contained in a hydrophobic organic solventforming a continuous phase (oil phase) and that an aqueous solution of avinyl-based monomer is prepared for a dispersing phase and awater-in-oil (W/O) type emulsion is prepared in the dispersion tank inadvance. The polymerization reaction is initialized feeding thewater-in-oil (W/O) type emulsion into the continuous stirred tankreactor continuously.

The inverse suspension polymerization according to the present inventionis preferably carried out under stirring. As the stirring blade, ananchor blade and a paddle blade are preferable, and a paddle blade isparticularly preferred. Generally, suspension polymerization isinfluenced by stirring power. If the stirring power is excessively low,polymer microparticles having a desired particle size cannot be obtainedor it is impossible to inhibit an aqueous solution of monomers frommerging, and, as a result, problems may arise, such as that perfectlyspherical microparticles can not be obtained or that many aggregatedparticles are formed.

In the present invention, the stirring power per unit volume in thecontinuous stirred tank reactor is preferably 0.5 kw/m³ or higher, andparticularly 1.0 kw/m³ or higher.

In the inverse suspension polymerization according to the presentinvention, a redox polymerization initiator including an oxidizing agentand a reducing agent is used as a polymerization initiator. A redoxreaction makes it possible to proceed a polymerization initiation at alow temperature, increase the concentration of a vinyl-based monomer ina polymerization reaction liquid and increase the polymerization rate.Therefore, the productivity can be improved and the molecular weight ofa polymer formed can be higher.

The oxidizing agent is preferably an oil-soluble oxidizing agent. Asmentioned above, a hydrophobic organic solvent in which a dispersionstabilizer is dissolved is used as a continuous phase (oil phase) in theinverse suspension polymerization. The oil-soluble oxidizing agent meansan oxidizing agent that is capable of being dissolved in the continuousphase.

Particularly, the oil-soluble oxidizing agent is preferably a compoundhaving an octanol/water partition coefficient (logPow) provided inJapanese Industrial Standards Z7260-107 or OECD TEST Guideline 107 ofpreferably −1.4 or more, more preferably 0.0 or more, and furtherpreferably 1.0 or more.

Specific example thereof includes an organic peroxide such as tert-butylhydroperoxide (logPow=1.3), di-tert-butyl hydroperoxide, tert-hexylhydroperoxide, di-tert-amyl hydroperoxide, cumene hydroperoxide(logPow=2.2), dicumyl peroxide (logPow=5.5), tert-butyl cumyl peroxide,tert-butyl peroxy pivalate, benzoyl peroxide (logPow=3.5), and lauroylperoxide. Among these, tert-butyl hydroperoxide and cumene hydroperoxideare preferable. The particular preferred is cumene hydroperoxide.

Conventionally known reducing agents can be used as the reducing agent.Among these, sodium sulfite, sodium hydrogensulfite, and sodiumhydrosulfite are preferable. Particularly preferred is sodiumhydrosulfite.

The method for feeding the oxidizing agent and reducing agent ispreferably one in which any one of the oxidizing agent and reducingagent is charged into the water-in-oil (W/O) type emulsion prepared inthe dispersion tank to mix therewith, on the other hand, other initiatoris supplied to the continuous stirred tank reactor to initiatepolymerization. Particularly preferred is a method in which an oxidizingagent is mixed with the water-in-oil (W/O) type emulsion in advance anda reducing agent is supplied to the continuous stirred tank reactor.

The amount of the polymerization initiator to be used may be adjustedaccording to the types of the vinyl-based monomer and the particle sizeand molecular weight of the resultant polymer microparticles. The amountof the oxidizing agent is in the range from 0.001 to 0.15 mol, andparticularly from 0.003 to 0.07 mol based on 100 mol of the total of thevinyl-based monomer.

Additionally, the ratio of the oxidizing agent and the reducing agent isnot particularly limited. The molar ratio of the water-soluble oxidizingagent to the water-soluble reducing agent is preferably 1.0 to0.25-15.0, and particularly 1.0 to 1.0-10.0.

If the ratio is outside that range, the unfavorable may be occurred.Example thereof includes a generation of aggregates caused by loweringof the reaction rate of monomers, shortening of the chain of polymerconstituting particles, remaining of a catalyst after the completion ofpolymerization; and the like.

In the inverse suspension polymerization according to the presentinvention, the temperature of the reaction liquid at the time ofstarting the polymerization is preferably in the range from 0° C. to 40°C., more preferably from 5° C. to 30° C., and particularly from 10° C.to 25° C. If the reaction start temperature is lower than 0° C.,freezing of a polymerization facility or a reaction solution becomes aproblem and a large cost is required for cooling. On the other hand, ifthe reaction start temperature exceeds 40° C., it is necessary, from asafety aspect, to reduce the amount of monomers to be fed, resulting ina large production cost.

When the continuous stirred tank reactors are serially-connected, aresidence time in the reactor can be shortened and a frequency ofcoalescence between the polymer microparticles and a vinyl-based monomerin the reactor can be reduced, thereby generation of aggregates duringthe polymerization can be prevented. It is preferable to use two andmore tank reactors serially-connected, and more preferable to use twoand more tank reactors serially-connected.

In the inverse suspension polymerization according to the presentinvention, it is desirable to prevent generation of aggregates duringthe polymerization by reducing the residence time in each reactor asshort as possible to decrease the frequency of coalescence between thepolymer microparticles and a vinyl-based monomer in the reactor. Inaddition, when the residence time is shortened, the reactor volume canbe reduced, and broadening of particle size distribution caused byscale-up can be also prevented.

For each reactor, the residence time of at least the first reaction tankis preferably 10 minutes or shorter, more preferably 5 minutes orshorter, and particularly 30 seconds or shorter. If the residence timeexcesses beyond 10 minutes, generation of aggregates during thepolymerization may be increased. On the other hand, if the residencetime is excessively short, a polymerization rate is reduced and morereactor stages are required. Therefore, it is preferred that theresidence time is 15 seconds and longer.

Further, for the purpose of preventing from forming aggregates duringthe polymerization caused by coalescence between the monomers andbetween the polymer microparticles and a monomer as well as coarsesingle particles in the reactor, the volume ratio of the dispersingphase in the reactor is preferably in the range from 5% to 30%, and morepreferably from 20% to 25%. If the volume ratio of the dispersing phasein the reactor exceeds 30%, the amount of the generated aggregatesduring the polymerization may be increased. On the other hand, if thevolume ratio of the dispersing phase is less than 5%, the productivityis reduced, being undesirable.

If oxygen is existed during the redox inverse suspension polymerization,the polymerization may be inhibited. Therefore, it is desired to removeoxygen.

Examples of the removing oxygen include a replacing of oxygen withnitrogen in the system by nitrogen-bubbling. A vinyl-based monomerpreparing tank for preparation of the vinyl-based monomer material or avinyl-based monomer supply tank may be deaerated in advance, but thereis a risk of abnormal polymerization in this way. Further, thevinyl-based monomer can be deaerated by flowing nitrogen into a supplyline of the vinyl-based monomer to the dispersion tank; however,adjustment of the size of monomer drops by changing the pore size ofmicroporous membrane may not always be effective because monomer dropsare microparticulated by mixing with nitrogen when nitrogen is providedinto the membrane emulsification apparatus. Accordingly, it ispreferable to deaerate by nitrogen-bubbling after passing through themicroporous membrane.

In the production of polymer microparticles, attachment of the polymerto a wall of the reactor often becomes a problem. The polymermicroparticles can be removed with a dispersion medium (continuousphase), therefore, it is preferable to continuously provide thedispersion medium on the wall of the gas phase of the reactor and washthe wall with the medium. The method to provide the dispersion medium(continuous phase), which is a wash, is preferably a way using a spray,a ring etc., and more preferably a way that spray the wash onto the wallsurface by providing the wash to a dispersion plate attached to astirring shaft.

In the production method of the present invention, the average particlesize of the resultant polymer microparticles is preferably in the rangefrom 2 to 150 μm, more preferably from 2 to 100 μm, and furtherpreferably from 5 to 70 μm. If the average particle size is smaller than2 μm, the slipping property or blocking preventing function may beinsufficient. If it exceeds 150 μm, an problem such as unfavorableappearance, deterioration of touch feeling and lowering of the strengthafter incorporating materials may be occurred. When the size of thepolymer microparticles becomes smaller, the stabilizing effect of thedispersion stabilizer comes to be needed more because the interfacialarea between a continuous phase and a dispersing phase becomes larger.

As to the size of the polymer microparticles, the size under a conditionwhere the particles are used becomes important. When the polymermicroparticles are used as water-swollen particles, it is preferablethat the size when the particles are swollen with water be within theabove-mentioned range.

The polymer microparticles are preferably crosslinked. As mentionedabove, the crosslinking structure of a polymer constituting themicroparticles is based on copolymerization of a multifunctionalvinyl-based monomer.

It is also possible to adjust the degree of crosslinking by reacting acrosslinking agent after polymerizing a vinyl-based monomer having afunctional group by the inverse suspension polymerization. For example,there is a method in which polymer microparticles of a monomer having acarboxyl group is subjected to crosslinking with ethylene glycoldiglycidyl ether.

Alternatively, a polymer can be crosslinked by a known method such asionic bond type crosslinking via a multivalent metal ion and covalentbond type crosslinking in which crosslinking is achieved by applicationof radiation.

When the polymer microparticles according to the above-mentionedcrosslinking method are having a crosslink density of 0.5% or more bymol, the particle can exert its characteristics in various applicationsmentioned above. Therefore, it is preferable that the polymermicroparticles have a crosslink density of 0.5% or more by mol.

After forming a dispersion liquid of polymer microparticles by inversesuspension polymerization according to the present invention, a drypowder of the polymer microparticles can be obtained using a knownmethod. A method of obtaining a dry powder by heating the dispersionliquid as it is and then removing volatile components under a reducedpressure reduction, and a method comprising removing a dispersionstabilizer, unreacted monomers and the like by performing solid-liquidseparation by filtration or centrifugal separation, and washing, andthen performing drying, are selected. To perform a washing step isdesirable because the primary dispersion property of the microparticlesafter drying increases.

Additionally, it is desirable to remove water before drying byazeotropic distillation or the like since the dispersing phase containswater. When the water is removed beforehand, it is possible to preventparticles from fusing at the time of drying and, as a result, theprimary dispersion property of the particles after drying increases.

According to the present invention, it is possible to smoothly producepolymer particles having an average particle size in a saturatedwater-swollen state of 2 to 100 μm and a content ratio of particleshaving a particle size of 150 μm or larger in a saturated water-swollenstate of 1.0% or less by weight. Such polymer particles can demonstrateits characteristics remarkably in various applications.

Furthermore, it is also possible to produce polymer particles having awater absorption ratio of 5 to 50 times, an average particle size in asaturated water-swollen state of 5 to 70 μm, and a content ratio ofparticles having a particle size of 150 μm or larger in a saturatedwater-swollen state of 0.3% or less by weight. The polymer will becomepolymer particles that lead to excellent characteristics in variousapplications.

It is noted that the water absorption ratio of the polymermicroparticles, the average particle size in a state where the particleis saturated and swollen with water, and the content of a particlesaturated and swollen with water having a particle size of 150 μm orlarger in the present specification are values measured or determined bythe methods described in the following Example section.

Examples

Hereinafter, the present invention is described in detail usingExamples. In the following description, “part” means part by weight and“%” means % by weight.

Production Example 1 Production of Macromonomer Compositions UM-1 andUM-1HP

The temperature of an oil jacket of a 1,000-mL pressuring stirring tanktype reactor with the oil jacket was kept at 240° C.

A monomer mixture liquid prepared in proportions of 75.0 parts of laurylmethacrylate (hereinafter referred to as “LMA”) and 25.0 parts ofacrylic acid (hereinafter referred to as “AA”) as a monomer, 10.0 partsof methyl ethyl ketone (hereinafter referred to as “MEK”) as apolymerization solvent, and 0.45 part of di-tert-butyl peroxide(hereinafter referred to as “DTBP”) as a polymerization initiator wascharged into a tank for starting material.

Feed of the monomer mixture liquid in the tank for starting material toa reactor was started, and the feed of the monomer mixture liquid andextraction of a reaction mixture liquid were carried out so that theweight of the contents within the reactor would be 580 g and the averageresidence time would be 12 minutes. The temperature in the reactor andthe pressure in the reactor were adjusted to 235° C. and 1.1 MPa,respectively. The reaction mixture liquid extracted from the reactor wasdepressurized to 20 kPa and continuously fed to a thin-film evaporatormaintained at 250° C. Thereby a macromonomer composition from which amonomer, a solvent and the like was distilled was discharged. Themonomer, the solvent and the like that were distilled were cooled with acondenser and collected as a distillate. A time when 60 minutes hadelapsed from a time when the temperature in the reactor had becomestable at 235° C. after the start of the feed of the monomer mixtureliquid was defined as a collection starting point, from which thereaction was continued for 48 minutes and then a macromonomercomposition UM-1 was collected. During this period, 2.34 kg of themonomer mixture liquid was fed to the reactor, and 1.92 kg of themacromonomer composition was collected from the thin-film evaporator.Moreover, 0.39 kg of the distillate was collected in a distillationtank.

The distillate was analyzed by gas chromatography, and it was found that100 parts by weight of the distillate contained 31.1 parts of LMA, 16.4parts of AA, and 52.5 parts of the solvent and others.

From the amount and the composition of the monomer mixture liquid fed,the amount of the macromonomer composition collected, and the amount andthe composition of distillate collected, the reaction rate of themonomer was calculated to be 90.2%, and the constitutional monomercomposition ratio of the macromonomer composition UM-1 was calculated tobe LMA to AA=76.0 to 24.0 (weight ratio).

The molecular weight of the macromonomer composition UM-1 was measuredby gel permeation Chromatography (hereinafter referred to as “GPC”)using tetrahydrofuran as an eluate and the polystyrene-equivalent weightaverage molecular weight (hereinafter referred to as “Mw”) and thepolystyrene-equivalent number average molecular weight (hereinafterreferred to as “Mn”) were 3,800 and 1,800, respectively. Additionally,the concentration of terminal ethylenically unsaturated bond in themacromonomer composition was determined through ¹H-NMR measurement ofthe macromonomer composition. From the concentration of terminalethylenically unsaturated bond obtained by ¹H-NMR measurement, Mnobtained by GPC, and the constitutional monomer ratio, the introductionratio of the terminal ethylenically unsaturated bond (hereinafterreferred to as “F value”) of the macromonomer composition UM-1 wascalculated to be 97%.

The produced macromonomer composition UM-1 was dissolved by heating inan appropriate amount of n-heptane, and then n-heptane was added so thatthe solid concentration would become 30.0%±0.5%. Thus, n-heptanesolution UM-1HP containing the macromonomer composition UM-1 wasproduced. The solid concentration was measured from a heat-calculatedfraction after heating at 150° C. for one hour.

As to starting materials including a monomer, a polymerization solvent,a polymerization initiator and the like, commercially availableindustrial products were used as received without performing anytreatment, such as purification.

Example 1 Production of Polymer Microparticles RT-1

For the preparation of the oil phase, the container was charged with 6.3parts (1.9 parts in terms of pure content of UM-1) of the UM-1HPproduced in Production Example 1 and 2.8 parts of sorbitan monooleate(“REODOL AO-10” manufactured by KAO Corp.) as a dispersion stabilizerand 554.5 parts of n-heptane as a polymerization solvent, which werestirred and mixed for 30 minutes while the solution was kept at atemperature of 40° C., and then the mixture was cooled to 20° C.

On the other hand, for the preparation of the aqueous phase, intoanother container were charged 100.0 parts of AA, 15.9 parts (equivalentto 2.0 mol% relative to a monofunctional monomer) of polyethylene glycoldiacrylate (“ARONIX M-243” manufactured by TOAGOSEI CO., LTD., averagemolecular weight 425), and 95.0 parts of ion exchange water, which werestirred to be dissolved uniformly. Furthermore, while the mixed liquidwas cooled so that the temperature thereof might be kept at 40° C. orlower, 70.8 parts of a 25% aqueous ammonia solution was added slowly toneutralize the mixed liquid. Thus, a monomer mixed liquid was obtained.

The prepared aqueous phase and the prepared oil phase were joined beforethe first dispersion tank and the mixture was supplied to a multistagedispersion tank. An emulsifier “ClearMix CLM-0.8S” manufactured by MTechnique Co., Ltd. was arranged in the first dispersion tank, and amembrane emulsification apparatus manufactured by SPG Technology Co.,Ltd. was arranged in the second dispersion tank. Shirasu porous glass(SPG) membrane (φ10×20 mm) was used for a microporous membrane in themembrane emulsification apparatus.

A reactor was equipped with a stirring system including one-tieredpitched paddle stirring blade, and further equipped with a thermometer,a nitrogen introduction tube, and a catalyst supply tube. Three of suchreactors (all have a capacity of 200 ml) were arranged in tandem.Polymerization initiator was supplied from a supply tube on the side ofthe reactor.

After setting the stirring revolution speed of the emulsifier at 2,400rpm, a pore size of the SPG membrane at 30 μm, and stirring blades ofeach tank reactor at 510 rpm, prepared oil phase was supplied at 300 gper minute, prepared aqueous phase was supplied at 150 g per minute, and“Percumyl H80” that is manufactured by NOF Corp. and is a n-heptanesolution of 0.027 part of cumene hydroperoxide and 1.3 part ofn-heptane) as an oil-soluble oxidizing agent was continuously suppliedto the emulsifier, which is the first dispersion tank, at 1.3 g perminute. Internal temperature of the emulsifier was kept at 20° C. Atthis time, the volume fraction of the dispersing phase in the reactiontank is 25%. After passage of a membrane emulsification apparatus,nitrogen was blown into to the water-in-oil (W/O) type emulsion withadjusted dispersed-drop diameter to remove oxygen in the dispersionliquid, and the liquid was provided into the reactor while overflowing.

To the first reaction tank, an aqueous solution of 0.18 part of sodium(Na) hydrosulfite and 1.3 part of ion exchange water was added at 1.4 gper minute through an addition port mounted at the side of the reactor.On each wall surface of the reactor, n-heptane was supplied at 14 g perminute using a dispersion plate attached to a stirring shaft. Internaltemperature of the first reaction tank was reached 35° C. at the timewhen three minutes had passed since the aqueous solution of sodiumhydrosulfite was supplied. Into the second reaction tank, the aboveheptane solution of Percumyl H80 was added at 1.3 g per minute. Also,into the third reaction tank, Percumyl H80 was added at 1.3 g perminute. The residence time for each reactor was 20 seconds.

When the in-oil dispersion liquid which is a mixed liquid of polymermicroparticles RT-1 and the oil phase was discharged from the reactor,the dispersion liquid was filtered using a filter having a mesh openingof 75 μm. Filterability was very good and the filtration wassuccessfully completed without occlusion until the end. When theattachment of a resin to the inner wall surface of the reactor waschecked after the discharge, the resin was slightly found at thevicinity of the liquid surface of the dispersion liquid and it wasconfirmed that the polymer microparticles RT-1 could be produced stably.

When a part of the in-oil dispersion liquid of RT-1 was sampled and wasobserved with a digital microscope (“KH-3000” manufactured by HIROX Co.,Ltd.) at a magnification of 420, spherical microparticles having adistribution centering approximately 10 to 20 μm were observed. Thephotograph thereof is shown in FIG. 1. No aggregated particles composedof particles united together were observed. For a sample prepared bydrying the in-oil dispersion liquid at 110° C. for one hour, the waterabsorption ratio (see the polymer microparticles analysis condition (2)below) was measured to be 20.2. When the dried sample was dispersed inan excessive amount of ion exchange water to be saturated and swollenand was observed at a magnification of 420, spherical microparticleshaving a distribution centering approximately 30 to 40 μm were observed.The photograph thereof is shown in FIG. 2. For thewater-saturated-swollen particles RT-1, particle size distributionmeasurement (see the polymer microparticles analysis condition (3)below) was performed using a laser diffraction scattering type particlesize distribution analyzer. The obtained particle size distribution hada single peak, and the water-saturated-swollen particle size was 35.2 μmbased on volume and 19.3 μm based on number. It was confirmed that thepolymer microparticles RT-1 had a water absorption capacity, keptspherical shape also when it was swollen due to water absorption, andwas primarily dispersed in water. Moreover, for a sample prepared byheating the dispersion liquid of RT-1, thereby azeotropically distillingwater and heptane contained in the particle to remove water to adehydration degree of 95%, followed by removal of the solvent andpowdering, the amount of a wet sieve residue (see the polymermicroparticles analysis condition (4) below) was measured to be 0.02%.The polymer microparticles RT-1 were confirmed to contain no coarseparticles greater than 150 μm also when they were saturated and swollenwith water after the azeotropic dehydration.

Example 2 Production of Polymer Microparticles RT-2

Production was conducted in the same conditions as those in Example 1,except that stirring revolution speed was 4,500 rpm and a pore size ofthe SPG membrane was 20 μm.

When a part of the in-oil dispersion liquid of RT-2 was sampled and wasobserved with a digital microscope (“KH-3000” manufactured by HIROX Co.,Ltd.) at a magnification of 420, spherical microparticles having adistribution centering approximately 5 to 10 μm were observed. Thephotograph thereof is shown in FIG. 3. No aggregated particles composedof particles united together were observed. For a sample prepared bydrying the in-oil dispersion liquid at 110° C. for one hour, the waterabsorption ratio (see the polymer microparticles analysis condition (2)below) was measured to be 18.1. When the dried sample was dispersed inan excessive amount of ion exchange water to be saturated and swollenand was observed at a magnification of 420, spherical microparticleshaving a distribution centering approximately 15 to 25 μm were observed.The photograph thereof is shown in FIG. 4. For thewater-saturated-swollen particles RT-2, particle size distributionmeasurement (see the polymer microparticles analysis condition (3)below) was performed using a laser diffraction scattering type particlesize distribution analyzer. The obtained particle size distribution hada single peak, and the water-saturated-swollen particle size was 19.1 μmbased on volume and 15.5 μm based on number. Therefore, the ratiobetween the average particle size based on volume and the averageparticle size based on number, indicating a degree of sharpness ofdistribution was 1.23, being small. The range of the particle sizedistribution was in the range from 9 to 51 μm. It was confirmed that thepolymer microparticles RT-2 have water absorbability, and maintain aspherical shape even after water-saturated and swollen state, andindicate primary dispersion in water.

Moreover, for a sample prepared by heating the RT-2, therebyazeotropically distilling water and heptane contained in the particlesto remove water to a dehydration degree of 95%, followed by removal ofthe solvent and powdering, the amount of a wet sieve residue wasmeasured to be 0.01% by weight. The microparticles RT-2 were confirmedto contain almost no coarse particles greater than 150 μm also when theyhad been saturated and swollen with water after the azeotropicdehydration.

When the in-oil dispersion liquid which is a mixed liquid of polymermicroparticles RT-2 and the oil phase was discharged from the reactor,the dispersion liquid was filtered using a filter having a mesh openingof 75 μm. Filterability was very good and the filtration wassuccessfully completed without occlusion until the end. When theattachment of a resin to the inner wall surface of the reactor waschecked after the discharge, the resin was slightly found at thevicinity of the liquid surface of the dispersion liquid and it wasconfirmed that the polymer microparticles RT-2 could be produced stably.

Example 3 Production of Polymer Microparticles RT-3

The production was performed in the same conditions as those in Example2 except that the residence time in the first reaction tank was 1 minuteand that the supply of the water-in-oil (W/O) type emulsion and thesupply of the polymerization initiator were ⅓ of the production case forRT-2. As a result, polymer microparticles were obtained having a swollenparticle size, which is an average particle size based on volume of 14.1um and the ratio between the average particle size based on volume andthe average particle size based on number of 1.23.

When the in-oil dispersion liquid which is a mixed liquid of polymermicroparticles RT-3 and the oil phase was discharged from the reactor,the dispersion liquid was filtered using a filter having a mesh openingof 75 μm. Filterability was very good and the filtration wassuccessfully completed without occlusion until the end. When theattachment of a resin to the inner wall surface of the reactor waschecked after the discharge, the resin was slightly found at thevicinity of the liquid surface of the dispersion liquid and it wasconfirmed that the polymer microparticles RT-3 could be produced stably.

Example 4 Production of Polymer Microparticles RT-4

The production was performed in the same conditions as those in Example3 except that the residence time in the first reaction tank was 5minutes and that the volume of the first reaction tank was 1,000 ml. Asa result, polymer microparticles were obtained having a swollen particlesize, which is an average particle size based on volume of 15.0 μm andthe ratio between the average particle size based on volume and theaverage particle size based on number of 1.25.

When the in-oil dispersion liquid which is a mixed liquid of polymermicroparticles RT-4 and the oil phase was discharged from the reactor,the dispersion liquid was filtered using a filter having a mesh openingof 75 μm. Filterability was very good and the filtration wassuccessfully completed without occlusion until the end. When theattachment of a resin to the inner wall surface of the reactor waschecked after the discharge, the resin was slightly found at thevicinity of the liquid surface of the dispersion liquid and it wasconfirmed that the polymer microparticles RT-4 could be produced stably.

Example 5 Production of Polymer Microparticles RT-5

The production was performed in the same conditions as those in Example3 except that the residence time in the first reaction tank was 10minutes and that the volume of the first reaction tank was 2,000 ml. Asa result, polymer microparticles were obtained having a swollen particlesize, which is an average particle size based on volume of 14.2 μm andthe ratio between the average particle size based on volume and theaverage particle size based on number of 1.32.

When the in-oil dispersion liquid which is a mixed liquid of polymermicroparticles RT-5 and the oil phase was discharged from the reactor,the dispersion liquid was filtered using a filter having a mesh openingof 75 μm. Filterability was very good and the filtration wassuccessfully completed without occlusion until the end. When theattachment of a resin to the inner wall surface of the reactor waschecked after the discharge, the resin was slightly found at thevicinity of the liquid surface of the dispersion liquid and it wasconfirmed that the polymer microparticles RT-5 could be produced stably.

Example 6 Production of Polymer Microparticles RT-6

The production was performed in the same conditions as those in Example3 except that the residence time in the first reaction tank was 30minutes, that the volume of the first reaction tank was 3,000 ml andthat the supply of the water-in-oil (W/O) type emulsion and the supplyof the polymerization initiator were ½ of the production case for RT-3.As a result, polymer microparticles were obtained having a swollenparticle size, which is an average particle size based on volume of 14.2μm and the ratio between the average particle size based on volume andthe average particle size based on number of 1.24.

When the in-oil dispersion liquid which is a mixed liquid of polymermicroparticles RT-6 and the oil phase was discharged from the reactor,the dispersion liquid was filtered using a filter having a mesh openingof 75 μm. Filterability was very good and the filtration wassuccessfully completed without occlusion until the end. When theattachment of a resin to the inner wall surface of the reactor waschecked after the discharge, substantial attachment was confirmed at thearea having contact with a liquid level of the dispersion liquid and atan outlet port pipe of the tank.

Example 7 Production of Polymer Microparticles RT-7

The production was performed in the same conditions as those in Example3 except that the residence time in the first reaction tank was 60minutes, that the volume of the first reaction tank was 3,000 ml andthat the supply of the water-in-oil (W/O) type emulsion and the supplyof the polymerization initiator were ¼ of the production case for RT-3.As a result, polymer microparticles were obtained having a swollenparticle size, which is an average particle size based on volume of 13.4μm and the ratio between the average particle size based on volume andthe average particle size based on number of 1.31.

When the in-oil dispersion liquid which is a mixed liquid of polymermicroparticles RT-7 and the oil phase was discharged from the reactor,the dispersion liquid was filtered using a filter having a mesh openingof 75 μm. Filterability was very good and the filtration wassuccessfully completed without occlusion until the end. When theattachment of a resin to the inner wall surface of the reactor waschecked after the discharge, substantial attachment was confirmed at thearea having contact with a liquid level of the dispersion liquid and atan outlet port pipe of the tank.

Example 8 Production of Polymer Microparticles RT-8

The production was performed in the same conditions as those in Example2 except that the volume fraction of the dispersing phase in thereaction tank was 30%. As a result, polymer microparticles were obtainedhaving a swollen particle size, which is an average particle size basedon volume of 18.5 μm, and a particle size based on number of 11.8 μm.Therefore, the ratio between the average particle size based on volumeand the average particle size based on number was calculated to be 1.57,being large and the particle size was in the range from 8 to 262 μm.

Example 9 Production of Polymer Microparticles RT-9

The production was performed in the same conditions as those in Example2 except that “Perbutyl H69” manufactured by NOF Corp. (a 69% solutionof tert-butyl hydroperoxide) was used as the oxidizing agent. As aresult, polymer microparticles were obtained having a swollen particlesize, which is an average particle size based on volume of 19.2 μm, anda particle size based on number of 14.7 μm. Therefore, the ratio betweenthe average particle size based on volume and the average particle sizebased on number was calculated to be 1.31, being large and the particlesize was in the range from 9 to 133 um.

Example 10 Production of Polymer Microparticles RT-10

Ammonium persulfate was used as the oxidizing agent. The production wasperformed in the same conditions as those in Example 3 except that theresidence time in the first reaction tank was 30 minutes, that thevolume of the first reaction tank was 3,000 ml and that the supply ofthe water-in-oil (W/O) type emulsion and the supply of thepolymerization initiator were ½ of the production case for RT-3. As aresult, polymer microparticles were obtained having a swollen particlesize, which is an average particle size based on volume of 11.5 μm, aparticle size based on number of 8.60 μm, the ratio between the averageparticle size based on volume and the average particle size based onnumber of 1.34, and the particle size range from 5 to 34 μm.

When the in-oil dispersion liquid which is a mixed liquid of polymermicroparticles RT-10 and the oil phase was discharged from the reactor,the dispersion liquid was filtered using a filter having a mesh openingof 75 μm. Filterability was very good and the filtration wassuccessfully completed without occlusion until the end. When theattachment of a resin to the inner wall surface of the reactor waschecked after the discharge, substantial attachment was confirmed at thearea having contact with a liquid level of the dispersion liquid and atan outlet port pipe of the tank.

Comparative Example 1 Production of Polymer Microparticles RT-11

The production was performed in the same conditions as those in Example3 except that a tubular reactor was used instead of the tank reactor.And the residence time was 1 minute which is the same as that in Example3. As a result, polymer microparticles were obtained having a swollenparticle size, which is an average particle size based on volume of 14.7μm and the ratio between the average particle size based on volume andthe average particle size based on number of 1.31. The first reactiontube and an outlet port pipe of the reaction tube were occluded 60minutes after the initiation of polymerization.

Comparative Example 2 Production of Polymer Microparticles RT-12

The production was performed in the same conditions as those in Example2 except that the aqueous phase was supplied to the reaction tankwithout pre-emulsification. As a result, gel was generated in thereaction tank immediately after the initiation of polymerization, thusthe polymerization was aborted.

TABLE 1 Residence time Volume fraction Volume based Ratio of volume infirst in dispersing Oxidizing Polymerization average size based toreaction tank phase agent System (μm) solid based Example 1 20 seconds25 vol % Percumyl H Continuous stirred 35.2 1.82 tank reactor Example 220 seconds 25 vol % Percumyl H Continuous stirred 19.1 1.23 tank reactorExample 3  1 minute 25 vol % Percumyl H Continuous stirred 14.1 1.23tank reactor Example 4  5 minutes 25 vol % Percumyl H Continuous stirred15 1.25 tank reactor Example 5 10 minutes 25 vol % Percumyl H Continuousstirred 14.2 1.32 tank reactor Example 6 30 minutes 25 vol % Percumyl HContinuous stirred 14.2 1.24 tank reactor Example 7 60 minutes 25 vol %Percumyl H Continuous stirred 13.4 1.31 tank reactor Example 8 20seconds 30 vol % Percumyl H Continuous stirred 18.5 1.57 tank reactorExample 9 20 seconds 25 vol % Perbutyl H Continuous stirred 19.2 1.31tank reactor Example 10 30 minutes 25 vol % Ammonium Continuous stirred11.5 1.34 persulfate tank reactor Comparative  1 minute 25 vol %Percumyl H Tubular reactor 14.7 1.31 Example 1 Comparative 20 seconds 25vol % Percumyl H Continuous stirred No data due No data due Example 2tank reactor to gelation to gelation

The polymer microparticles analysis conditions (1) to (4) used inExamples are as follows.

(1) Solid Concentration

The weight (a) of about 1 g of a sample was measured, the weight (b) ofa residue after drying in a windless oven at a temperature of 150° C.for 60 minutes was measured, and then the solid concentration wascalculated by the following equation. For the measurement a weighingbottle was used. Other operations were performed in accordance with JISK0067-1992 (Test methods for loss and residue of chemical products).

Solid concentration (%)=(b/a)×100

(2) Water Absorption Ratio

The water absorption ratio was measured according to the followingmethod. The measuring device is illustrated in FIG. 5.

The measuring device is composed of <1> to <3> shown in FIG. 3.

<1> is consisting of a burette 1 having a branch pipe for airventilation, a pinch cock 2, a silicone tube 3, and apolytetrafluoroethylene tube 4.

In <2>, a supporting cylinder 8 having many holes in its bottom ismounted on a funnel 5, and a filter paper 10 for device is mountedthereon.

In <3>, a sample 6 of the polymer microparticles is inserted into twofilter papers 7 for fixing sample, and the filter papers for fixingsample are fixed with an adhesive tape 9. All the filter papers to beused are “ADVANTEC No.2” having an inner diameter of 55 mm.

<1> and <2> are linked with the silicone tube 3.

The levels with respect to the burette 1 of the funnel 5 and thesupporting cylinder 8 are fixed, and the lower end of thepolytetrafluoroethylene tube 4 disposed within the burette branch pipeand the bottom of the supporting cylinder 8 are set to be at the samelevel (dotted line in FIG. 3).

The measuring method is described below.

The pinch cock 2 in <1> was released, and ion exchange water was chargedfrom the top of the burette 1 through the silicone tube 3 so that thespace from the burette 1 to the filter paper 10 for device was filledwith ion exchange water 12. Subsequently, the pinch cock 2 was closedand air was removed through the polytetrafluoroethylene tube 4 connectedto the burette branch pipe with a rubber stopper. Thus, a condition wasobtained such that ion exchange water 12 was continuously fed from theburette 1 to the filter paper 10 for device.

After that, excess ion exchange water 12 which oozed from the filterpaper 10 for device was removed, and then a read graduation (a) of theburette 1 was recorded.

A dry powder was sampled in an amount of 0.1 to 0.2 g, and then thepowder was placed uniformly on the center of the filter paper 7 forfixing sample as illustrated in <3>. Another filter paper was used tosandwich the sample and the two filter papers were adhered with anadhesive tape 9 to fix the sample. The filter papers between which thesample was fixed were put on the filter paper 10 for device asillustrated in <2>.

Subsequently, a read graduation (b) of the burette 1 after a lapse of 30minutes from a time when a lid 11 was put on the filter paper 10 fordevice was recorded.

The total (c) of the water absorption of the sample and the waterabsorption of the two filter papers 7 for fixing sample was calculatedby (a−b). By the same operation, the water absorption (d) of only thetwo filter papers 7 containing no water-absorptive polymer sample wasmeasured.

The above-mentioned operations were performed and a water absorptionratio was calculated from the following equation. As to the solidconcentration to be used for the calculation, a value measured by themethod (1) was used.

Water absorption ratio (times)=(c−d)/{Weight of sample (g)×(Solidconcentration (%)/100)}+100/(Solid concentration (%))

(3) Water-Swollen Particle Size

To 0.02 g of a sample for measurement was added 20 ml of ion exchangewater, followed by shaking well. Thus, the sample was disperseduniformly. For a dispersion liquid resulting from dispersion continuedfor 30 minutes or more in order to bring the polymer microparticles intoa water-saturated-swollen state, the particle size distribution wasmeasured after one-minute application of ultrasonic wave by using alaser diffraction scattering type particle size distribution analyzer(“MT-3000” manufactured by NIKKISO CO., LTD.). Ion exchange water wasused as a circulated dispersion medium used in the measurement and therefractive index of the dispersion was adjusted to 1.53. The mediandiameter (μm) was calculated from the particle size distribution onvolume basis obtained by the measurement, and it was defined as awater-swollen particle size.

(4) Measurement of Amount of Particle having Water-Swollen Particle Sizeof 150 μm or Larger (a Wet Sieving Residue Method)

Measurement was performed in accordance with JIS K 0069-1992 (testmethod for sieving of chemical products).

A sample in an amount corresponding to 50 g in terms of solidconcentration was weighed and ethanol was added thereto in the sameamount as the sample to loosen well. Then the liquid was poured slowlyinto 3.0 liters of ion exchange water under stirring and stirred for 30minutes to prepare a water-swollen dispersion liquid of the sample.After confirmation of the uniform dispersion, the dispersion liquid waspoured onto a sieve having a diameter of 70 mm and a mesh opening of 150μm and allowed to pass therethrough. The residue on the sieve was washedwith a sufficient amount of water while taking care that the residuedoes not spill off. Subsequently, the sieve after measurement was driedin a circulation dryer at a temperature of 150° C. for 30 minutes andcooled in a desiccator, and then the weight of the sieve after drying(the total weight of the sieve and the residue) was measured.

The wet sieve residue (%) calculated by the following formula wasdefined as the amount of particle having a water-swollen particle sizeof 150 μm or larger. Operations other than those described above wereperformed in accordance with JIS K 0069-1992 (test method for sieving ofchemical products).

Wet sieve residue (%)=(Weight of sieve after test−Weight ofsieve)/{(Weight of sample used×(Solid concentration/100))}×100

Clearly from the results above, attachment of the resin to a wall of thereactor during polymerization was not observed and filtability of thepolymer slurry was favorable in the present production method. And itwas confirmed that polymer microparticles uniform in particle size couldbe produced in a good productivity without the occurrence of particleaggregation.

On the other hand, in Comparative Example 1 wherein a tubular reactorwas used, attachment to the pipe caused by aggregation of polymermicroparticles was occurred with progress of the polymerization, andthen, inside of the reaction tube was occluded in a short time after theinitiation of the reaction.

INDUSTRIAL APPLICABILITY

According to the production method of the present invention, ahigh-quality spherical hydrophilic polymer microparticles remarkablyhigher uniform in particle size than those by conventional technologiescan be produced at high productivity while keeping high dispersionstability and polymerization stability without causing aggregation,clumping and adhesion to a polymerization apparatus of particles duringor after polymerization. Moreover, according to the production method ofthe present invention, even if a particle having a high degree ofcrosslinking is produced using a large amount of a multifunctionalvinyl-based monomer, a high-quality hydrophilic crosslinked polymermicroparticles uniform in particle size can be produced at highproductivity without causing aggregation, clumping and adhesion to apolymerization apparatus of particles.

1. A method for the production of polymer microparticles by inversesuspension polymerization of a vinyl-based monomer, said methodcomprising: preparing in a dispersing tank, a water-in-oil (W/O) typeemulsion in which an organic solvent is a continuous phase and anaqueous solution of a vinyl-based monomer is a dispersing phase, andconducting the inverse suspension polymerization while feeding saidwater-in-oil (W/O) type emulsion to a continuous stirred tank reactor.2. The method for the production of polymer microparticles according toclaim 1, wherein a redox polymerization catalyst comprising an oxidizingagent and a reducing agent is used as a polymerization initiator.
 3. Themethod for the production of polymer microparticles according to claim2, wherein said oxidizing agent is an oil-soluble oxidizing agent. 4.The method for the production of polymer microparticles according toclaim 1, wherein said reactor comprises at least two continuous stirredtank reactors serially-connected.
 5. The method for the production ofpolymer microparticles according to claim 1, wherein a residence time ofa reaction liquid in at least a first reaction tank is ten minutes orshorter.
 6. The method for the production of polymer microparticlesaccording to claim 1, wherein a ratio of said dispersing phase in eachreaction liquid in the respective reaction tank is 30% or less byvolume.
 7. The method for the production of polymer microparticlesaccording to claim 1, wherein said water-in-oil (W/O) type emulsion isprepared using a dispersing tank which has at least one stirringapparatus and at least one membrane emulsification apparatus.
 8. Themethod for the production of polymer microparticles according to claim7, wherein said water-in-oil (W/O) emulsion is deaerated after passingsaid membrane emulsification apparatus.
 9. The method for the productionof polymer microparticles according to claim 1, wherein a continuousphase component is continuously fed to a wall of a gas phase of saidcontinuous stirred tank reactor.
 10. The method for the production ofpolymer microparticles according to claim 2, wherein an oxidizing agentor a reducing agent is mixed with said water-in-oil (W/O) emulsion insaid dispersing tank.
 11. The method for the production of polymermicroparticles according to claim 1, wherein a water-in-oil (W/O)emulsior is prepared which has an average particle size of saiddispersing phase of 100 μm or less in said dispersing tank.
 12. Themethod for the production of polymer microparticles according to claim1, wherein a macromonomer having a radically polymerizable unsaturatedgroup at an end of a polymer derived from a vinyl-based monomer is usedas a dispersion stabilizer.
 13. The method for the production of polymermicroparticles according to claim 1, wherein at least one part of saidvinyl-based monomer has a polar group selected from the group consistingof a carboxyl group, a sulfone group and an amide group.
 14. The methodfor the production of polymer microparticles according to claim 1,wherein said vinyl-based monomer contains a multifunctional vinylmonomer having two or more radical polymerizable unsaturated groups. 15.The method for the production of polymer microparticles according toclaim 14, wherein a molar ratio of a monofunctional vinyl monomer andsaid multifunctional vinyl monomer is 100:0.1 to 100:10.
 16. The methodfor the production of polymer microparticles according to claim 1,wherein said polymer microparticles produced by inverse suspensionpolymerization are polymer microparticles having a crosslinking densityof 0.5% or more by mol.
 17. The method for the production of polymermicroparticles according to claim 1, wherein said polymer microparticlesproduced by inverse suspension polymerization are polymer microparticleswhich have an average particle size in a saturated water-swollen stateof 2 to 100 μm, and a content ratio of particles having a particle sizeof 150 μm or larger in a saturated water-swollen state of 1.0% or lessby weight.
 18. The method for the production of polymer microparticlesaccording to claim 1, wherein said polymer microparticles produced byinverse suspension polymerization are polymer microparticles which havea water absorption ratio of 5 to 50 times, an average particle size in asaturated water-swollen state of 5 to 70 μm, and a content ratio ofparticles having a particle size of 150 μm or larger in a saturatedwater-swollen state of 0.3% or less by weight.